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Materials Data on K2CO3 by Materials Project

K2CO3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a hexagonal planar geometry to six equivalent O2- atoms. All K–O bond lengths are 2.92 Å. In the second K1+ site, K1+ is bonded to six equivalent O2- atoms to form face-sharing KO6 octahedra. All K–O bond lengths are 2.71 Å. C4+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. All C–O bond lengths are 1.30 Å. O2- is bonded in a distorted single-bond geometry to four K1+ and one C4+ atom.

36 MATERIALS SCIENCE↗

Materials Data on K2CO3 by Materials Project

K2CO3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded to six O2- atoms to form face-sharing KO6 octahedra. There are a spread of K–O bond distances ranging from 2.66–2.84 Å. In the second K1+ site, K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.87–3.11 Å. C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.30 Å) and two longer (1.31 Å) C–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to five K1+ and one C4+ atom. In the second O2- site, O2- is bonded in a 1-coordinate geometry to four K1+ and one C4+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to five K1+ and one C4+ atom.

36 MATERIALS SCIENCE↗

Materials Data on K2CO3 by Materials Project

K2CO3 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.88–3.29 Å. In the second K1+ site, K1+ is bonded to six O2- atoms to form face-sharing KO6 octahedra. There are a spread of K–O bond distances ranging from 2.68–2.77 Å. C4+ is bonded in a trigonal planar geometry to three O2- atoms. All C–O bond lengths are 1.31 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to five K1+ and one C4+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to four K1+ and one C4+ atom.

36 MATERIALS SCIENCE↗

Microscopic 3D Graphene for High-Performance Supercapacitors with Ultra-High Areal Capacitance

Despite graphene being considered as an ideal supercapacitor electrode material, its use in commercial devices is limited because few methods exist to produce high-quality graphene at large scale and low-cost. We report a simple method to synthesize 3D graphene by graphenization of coal tar pitch with a K2CO3 catalyst. This produces 3D graphenes with high specific surface areas up to 2113 m2 g-1 and exceptional crystallinity (Raman ID/IG as low as ~ 0.15). The material has an outstanding specific capacitance of 182.6 F g-1 at a current density of 1.0 A g-1. This occurs at mass loading of 30 mg cm-2 which is 3 times higher than commercial requirements, yielding an ultra-high areal capacitance of 5.48 F cm-2. Moreover, the K2CO3 is recycled and reused over 10 cycles. The synthesis method and resulting electrocapacitive performance properties create new opportunities for using 3D graphene more broadly in practical supercapacitor devices.

Pham, Viet Hung↗

Upcycling Low Linear Density Polyethylene Waste into Turbostratic Graphene for High Mass Loading Supercapacitors

In this work, LLDPE was upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K2CO3) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400-950 °C without complete decomposition of the material. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800 m2g-1 and average Raman ID/IG and I2D/IG ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses an outstanding specific capacitance up to 175 Fg-1 at a mass loading of 20 mgcm-2, which is two times the commercial requirement, yielding an excellent areal capacitance of 3.5 Fcm-2. Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8% after 100,000 cycles at a current density of 4.0 Ag-1. Additionally, the KCl and K2CO3 were recycled and reused over 3 complete cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling not only waste LLDPE but also other varieties of PE to high value graphene materials.

Gao, Yuan [NETL Site Support Contractor, National ↗

Development of a prototype regenerable carbon dioxide absorber for portable life support systems

The design and development of a prototype carbon dioxide absorber using potassium carbonate (K2CO3) is described. Absorbers are constructed of thin, porous sheets of supported K2CO3 that are spirally wound to form a cylindrical reactor. Axial gas passages are formed between the porous sheets by corrugated screen material. Carbon dioxide and water in an enclosed life support system atmosphere react with potassium carbonate to form potassium bicarbonate. The potassium carbonate is regenerated by heating the potassium bicarbonate to 150 C at ambient pressure. The extravehicular mission design conditions are for one man for 8 h. Results are shown for a subunit test module investigating the effects of heat release, length-to-diameter ratio, and active cooling upon performance. The most important effect upon carbon dioxide removal is the temperature of the potassium carbonate.

Onischak, M.↗

An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

Keene, William C.↗

Understanding Europium and Terbium Speciation and Ion Pairing in Carbonate Complexes Using Advanced Spectroscopy Techniques

Lanthanide (Ln) elements are critical materials that are typically extracted/mined together. Their separation by solvent extraction from acidic media is well known; however, there are few studies in basic media with carbonate anions. We investigated the complexation of Eu(III) and Tb(III) carbonates as solids and solutions in alkaline K2CO3, wherein we sought to access a Tb(IV) carbonate complex through ozonolysis. L3-edge XANES of Eu and Tb carbonate solids, colorless solutions, and a red-hued Tb solution (obtained by ozonolysis) all showed Ln(III) cations. The absence of evidence for a Tb(IV) complex was confirmed through XAS and EPR analyses, despite the solution exhibiting a deep red color. For solids and solutions, EXAFS results indicate molecular Ln(III)-carbonato anions. In terms of the Eu(III) carbonate coordination number, the coordination does not change upon dissolution of the solid sample. Furthermore, EXAFS for the solutions revealed evidence for the association of potassium cations with the Ln(III)-carbonato anions. Furthermore, this direct observation of contact ion pairing by EXAFS at room temperature is rare. The insights into Ln(III) carbonate complexation and solution speciation afforded by XANES-EXAFS, FT-IR, and EPR provides perspectives that serve as benchmarks for future computational and experimental efforts focused on caustic-side solvent extraction of Ln(III) ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative Study of Flash and Acid Hydrolysis of Microalgae (Scenedesmus sp.) for the Recovery of Biochemicals and Production of Porous Biocarbon Nanosheets

An integrated biorefinery concept is a novel and economical process intensification methodology for efficient utilization of biomass components. In this research, microalgae (Scenedesmus sp.) slurry with biomass concentration of 8.5 wt.% was parallelly fractionated using two techniques: 'flash hydrolysis (FH)' and 'acid hydrolysis (AH)'. FH was performed at 240 degrees C with a residence time of 10 +/- 2 s in a continuous flow reactor, whereas AH was performed at 155 degrees C and reaction time of 15 min in a batch reactor. About 63% of microalgal biomass was solubilized in liquid hydrolysate through both FH and AH. However, AH had an advantage over FH in recovering microalgae proteins and carbohydrates. FAME recovery through solvent extraction from FH and AH derived wet solids (insoluble microalgae) was 40 and 63%, respectively. Finally, the FH- and AH-derived post extraction solid residue was thermally activated using K2CO3 to produce highly microporous biocarbon nanosheets with BET surface areas of 712 and 1289 m2 g-1, respectively. Overall, an integrated process was developed using two potential hydrolysis techniques to maximize utilization of microalgae components.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Upcycling Polyethylene Waste Into Hybrid Graphitic Porous Carbon Materials Used in High-Performance Zinc-Ion Hybrid Capacitors

Polyethylene (PE) waste is a challenge to upcycle into useful materials because this plastic tends to decompose into volatile compounds when heated at relatively low temperatures. In this work, we report a chemical process that addresses this challenge by converting mixtures of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE) waste into a hybrid graphitic porous carbon (HGPC) that can be used as a zinc-ion hybrid capacitor cathode. The process uses a low temperature thermal oxidation pre-treatment step, with assistance of an inert solid additive (KCl) to increase the effective surface area of the PE melt, to functionalize, cross-link, and stabilize the PE waste followed by carbonization and catalytic graphitization steps at higher temperatures with a potassium carbonate (K2CO3) catalyst. The PE waste derived HPGC (PW-HPGC) has a hybrid structure composed of graphene-like carbon nanosheets grown on the surface of carbon particles, high porosity with the Brunauer–Emmett–Teller (BET) specific surface area up to 1,763 m2g-1, and good graphitic degree with average Raman I2D/IG ratios of 0.53. When used as a cathode material for zinc-ion hybrid capacitors, this PW-HGPC exhibits an excellent specific capacity up to 126.7 mAhg-1 at high mass loading of 10 mgcm-2. Moreover, PW-HGPC exhibits remarkable cycling stability with capacity retention of >94% after 10,000 cycles at a current density of 2.0 A g-1.

hybrid graphitic porous carbon↗

High-temperature molten salt thermal energy storage systems for solar applications

Alkali and alkaline earth carbonate latent-heat storage salts, metallic containment materials, and thermal conductivity enhancement materials were investigated to satisfy the high temperature (704 to 871 C) thermal energy storage requirements of advanced solar-thermal power generation concepts are described. Properties of the following six salts selected for compatibility studies are given: three pure carbonates, K2CO3, Li2CO3 and Na2CO3; two eutectic mixtures, BaCO3/Na2CO3 and K2CO3/NaCO3, and one off-eutectic mixture of Na2CO3/K2CO3.

Petri, R. J.↗

High-temperature molten salt thermal energy storage systems for solar applications

Experimental results of compatibility screening studies of 100 salt/containment/thermal conductivity enhancement (TCE) combinations for the high temperature solar thermal application range of 704 deg to 871 C (1300 to 1600 F) are presented. Nine candidate containment/HX alloy materials and two TCE materials were tested with six candidate solar thermal alkali and alkaline earth carbonate storage salts (both reagent and technical grade of each). Compatibility tests were conducted with salt encapsulated in approx. 6.0 inch x 1 inch welded containers of test material from 300 to 3000 hours. Compatibility evaluations were end application oriented, considering the potential 30 year lifetime requirement of solar thermal power plant components. Analyses were based on depth and nature of salt side corrosion of materials, containment alloy thermal aging effects, weld integrity in salt environment, air side containment oxidation, and chemical and physical analyses of the salt. A need for more reliable, and in some cases first time determined thermophysical and transport property data was also identified for molten carbonates in the 704 to 871 C temperature range. In particular, accurate melting point (mp) measurements were performed for Li2CO3 and Na2CO3 while melting point, heat of fusion, and specific heat determinations were conducted on 81.3 weight percent Na2CO3-18.7 weight percent K2CO3 and 52.2 weight percent BaCO3-47.8 weight percent Na2CO3 to support future TES system design and ultimate scale up of solar thermal energy storage (TES) subsystems.

Petri, R. J.↗

Extinction of in-flight engine fuel-leak fires with dry chemicals

The dry chemicals discussed here are seen as having a greater weight effectiveness than the halons in current use for controlling fuel-leak fires, especially in the presence of high airflow rates. The commercial dry chemicals K2CO3, KHCO3, and KC2N2H3O3 are found to be more effective than CF2ClBr and CF3Br in delaying the hot-surface reignition of fuel-leak fires after initial extinguishment. Experimental dry chemical formulations of potassium dawsonite, KAl(OH)2CO3, and of KCl and KI are seen as being even more weight effective than the above-mentioned commercial dry chemicals. It is noted, however, that the suitability and effectiveness of dry chemicals in controlling engine nacele fires has not yet been demonstrated in test aircraft.

Altman, R. L.↗

Concentration of carbon dioxide by a high-temperature electrochemical membrane cell

The performance of a molten carbonate carbon dioxide concentrator (MCCDC) cell, as a device for removal of CO2 from manned spacecraft cabins without fuel expenditure, is investigated. The test system consists of an electrochemical cell (with an Li2CO3-38 mol pct K2CO3 membrane contained in a LiAlO2 matrix), a furnace, and a flow IR analyzer for monitoring CO2. Operation of the MCCDC-driven cell was found to be suitable for the task of CO2 removal: the cell performed at extremely low CO2 partial pressures (at or above 0.1 mm Hg); cathode CO2 efficiencies of 97 percent were achieved with 0.25 CO2 inlet concentration at 19 mA sq cm, at temperatures near 873 K. Anode concentrations of up to 5.8 percent were obtained. Simple cathode and anode performance equations applied to correlate cell performance agreed well with those measured experimentally. A flow diagram for the process is included.

Kang, M. P.↗

Replication of the Apparent Excess Heat Effect in a Light Water-Potassium Carbonate-Nickel Electrolytic Cell

Replication of experiments claiming to demonstrate excess heat production in light water-Ni-K2CO3 electrolytic cells was found to produce an apparent excess heat of 11 W maximum, for 60 W electrical power into the cell. Power gains range from 1.06 to 1.68. The cell was operated at four different dc current levels plus one pulsed current run at 1 Hz, 10% duty cycle. The 28 liter cell used in these verification tests was on loan from a private corporation whose own tests with similar cells are documented to produce 50 W steady excess heat for a continuous period exceeding hundreds of days. The apparent excess heat can not be readily explained either in terms of nonlinearity of the cell's thermal conductance at a low temperature differential or by thermoelectric heat pumping. However, the present data do admit efficient recombination of dissolved hydrogen-oxygen as an ordinary explanation. Calorimetry methods and heat balance calculations for the verification tests are described. Considering the large magnitude of benefit if this effect is found to be a genuine new energy source, a more thorough investigation of evolved heat in the nickel-hydrogen system in both electrolytic and gaseous loading cells remains warranted.

Niedra, Janis M.↗